两个磷光铱配合物的合成和性质研究

由于具有P=O键,二（二苯基膦酰）胺（tetraphenylimidodiphosphinateacid,Htpip）作为辅助配体引入Ir（Ⅲ）配合物中,可以提高配合物的电子迁移率和器件的效率。采用氟取代的2-（4-氟苯基）吡啶（F₄-ppy）为主配体、以Htpip和三氟甲基取代的Htfmtpip为辅助配体合成了2个铱配合物Ir（F₄-ppy）₂（tpip）和Ir（F₄-ppy）₂（tfmtpip）。晶体结构中Ir原子的配位几何构型均为八面体构型,Ir（F₄-ppy）₂（tpip）属于正交晶系Pbca空间群,而Ir（F₄-ppy）₂（tfmtpip）属于单斜晶系P2₁/c空间群。配合物都具有较好的热稳定性,Ir（F₄-ppy）₂（tpip）和Ir（F₄-ppy）₂（tfmtpip）的初始分解温度分别为385和395℃。配合物Ir（F₄-ppy）₂（tfmtpip）的氧化和还原峰较配合物Ir（F₄-ppy）₂（tpip）分别向正电压移动了大约0.134和0.12V,相应的HOMO和LUMO能级分别降低了0.14和0.43eV。在室温、1×10^-5mol·L^-1的CH₂Cl₂溶液中Ir（F₄-ppy）₂（tpip）和Ir（F₄-ppy）₂（tfmtpip）的最大磷光发射峰分别位于492和495nm,量子效率分别为9.2%和16.4%。结果表明在辅助配体上引入4个三氟甲基后不仅可以提高配合物的热稳定性和电化学稳定性,并且可以调控配合物的HOMO/LUMO能级和发光效率。     

一种红光铱配合物的合成和电致发光性能

以1-(4-三氟甲基苯基)异喹啉(tfmpiq)为主配体,二(二(4-三氟甲基苯基)膦酰)胺(tfmtpip)为辅助配体,成功合成了Ir髥配合物Ir(tfmpiq)2(tfmtpip),并得到了配合物的晶体结构。配合物Ir(tfmpiq)2(tfmtpip)的分解温度为373℃,具有良好的热稳定性。Ir(tfmpiq)2(tfmtpip)的发射光谱主要是MLCT发射,峰位置为613 nm,量子效率为3.7%,HOMO和LUMO轨道能级分别为-5.62和-3.54 e V。基于Ir(tfmpiq)2(tfmtpip)的器件ITO/TAPC(40 nm)/Ir(tfmpiq)2(tfmtpip)(x%)∶mCP(20 nm)/TmPyPB(40 nm)/LiF(1 nm)/Al(100 nm),当掺杂浓度为4%(w/w)时,器件达到最大功率效率和电流效率分别为5.73 lm·W-1和7.13 cd·A-1,而且器件在12.8 V的驱动电压下达到亮度10 542 cd·m-2。     

两种红光铱配合物的合成和电致发光性能研究

以二(二苯基磷酰)胺(Htpip)作为辅助配体,与主配体2-(2,4-二氟苯基)异喹啉和2-(4-三氟甲基苯基)异喹啉合成了红光铱磷光配合物Ir(dfpiq)2tpip和Ir(tfmpiq)2tpip并得到了晶体结构。在CH2Cl2中发射光谱主要是MLCT发射,峰位置分别为622和600 nm,量子效率分别为15%和17%,而HOMO/LUMO能级分别是-4.80/-2.58和-4.73/-2.57 eV。在1150~1300(V·cm-1)1/2电场范围,Ir(dfpiq)2tpip的电子迁移率为6.61~8.49×10-6cm2·V-1·s-1,Ir(tfmpiq)2tpip的电子迁移率为6.08~6.61×10-6cm2·V-1·s-1。ITO/TAPC(60 nm)/Ir-complex(15wt%):CBP(50 nm)/TPBi(60 nm)/LiF(1 nm)/Al(100 nm)中基于Ir(dfpiq)2tpip的器件最大安培效率和功率效率分别为4.71 cd·A-1和1.82 lm·W-1,12.0 V时达到的最大亮度为18 195 cd·m-2。基于Ir(tfmpiq)2tpip的器件最大安培效率和功率效率分别为3.47 cd·A-1和1.51 lm·W-1,12.4 V时达到的最大亮度为14 676 cd·m-2。     

利用吡啶衍生物主配体共轭效应调控铱配合物发光颜色(英文)

利用2-苯基吡啶及其衍生物为主配体、四苯基膦酰亚胺为辅助配体合成了3个铱配合物Ir(ppy)2tpip(Hppy:2-苯基吡啶,Htpip:四苯基膦酰亚胺)、Ir(npy)2tpip(Hnpy:2-(1-萘基)吡啶)和Ir(pnpy)2tpip(Hpnpy:2-(9-菲基)吡啶)。它们的结构通过1H NMR和MALDI-TOF质谱进行了表征,其中配合物Ir(ppy)2tpip还进一步通过晶体结构分析验证。主配体从苯环到萘环和菲环的改变增加了配合物的π共轭,减小了能级差,导致了3种配合物的磷光发射光谱从516 nm红移到600和633 nm(从绿光到红光),发光量子效率也从0.36增加到0.51和0.53。从量化计算的结果可以看出,这种共轭效应增加了主配体的电子密度,提高了配合物的LUMO能级。配合物结构和发射性质之间的关系规律为设计不同发光颜色的铱配合物提供了思路。     

三个绿光铱(Ⅲ)配合物的合成和光电性质

采用2-(4-三氟甲基苯基)吡啶(tfmppy)为主配体,分别以四(4-氟苯基)苯基膦酰亚胺(F-tpip)、四(4-甲氧基苯基)膦酰亚胺(MeO-tpip)和四(1-萘基)膦酰亚胺(tnin)为辅助配体合成了3个铱配合物((tfmppy)_2Ir(F-tpip)、(tfmppy)_2Ir(MeO-tpip)和(tfmppy)_2Ir(tnin))。其结构通过核磁氢谱、质谱、元素分析和单晶结构测定进行了验证。配合物(tfmppy)_2Ir(F-tpip)和(tfmppy)_2Ir(MeO-tpip)属于三方晶系P1空间群,配合物(tfmppy)_2Ir(tnin)属于三斜晶系R3c空间群。3个配合物都是绿光材料,具有类似的发光颜色和发光效率((tfmppy)_2Ir(F-tpip):λ_(em)=526 nm,Φ=0.52;(tfmppy)_2Ir(MeO-tpip):λ_(em)=523 nm,Φ=0.44;(tfmppy)_2Ir(tnin):λ_(em)=522 nm,Φ=0.48)。3个配合物的循环伏安曲线都显示出了良好的氧化还原性质。(tfmppy)_2Ir(F-tpip)、(tfmppy)_2Ir(MeO-tpip)和(tfmppy)_2Ir(tnin)的HOMO能级分别为-5.67、-6.08和-5.69 eV,其LUMO能级分别为-3.29、-3.61和-3.22 eV。     

两种基于氮杂环结构铱(Ⅲ)配合物的合成及有机电致发光性能

以苯基嘧啶/吡啶基嘧啶为母核, 同时引入2个三氟甲基(CF₃)合成了2-[3,5-二（三氟甲基）苯基]-5-氟基嘧啶(tfmphfppm)和2-[2,6-二（三氟甲基）-4-吡啶基]-5-氟基嘧啶(tfmpyfppm)主配体, 并以2-(5-苯基-1,3,4-噁二唑-2-)苯酚(pop)为辅助配体合成了2种铱(III)配合物Ir(tfmphfppm)₂(pop)和Ir(tfmpyfppm)₂(pop), 其发射光谱峰分别位于484和504 nm, 分别属于蓝绿光和绿光发射, 发光量子效率分别达到76%和89%. 由于氮杂环和2,5-二苯基-1,3,4-噁二唑基团的存在, 配合物具有较低的最低未占据分子轨道(LUMO)能级和较高的电子迁移率. 以2种 铱(III)配合物为发光中心制备的有机电致发光器件(OLED)显示了较好的器件性能, 其最大亮度(L_max)、 最大电流效率(η_{c, max})、 最大功率效率(η_{p, max})和最大外量子效率(EQE_max)分别为33379 cd/m², 76.55 cd/A, 31.59 lm/W和26.7%; 并且该器件显示了比较小的效率滚降, 在亮度为1000 cd/m²时, 器件的η_c仍然可以达到72.71 cd/A. 本文结果表明, 氮杂环、 2,5-二苯基-1,3,4-噁二唑和三氟甲基基团可以有效提高铱(Ⅲ)配合物的发光性能和电子迁移率, 从而提高器件的性能.     

含5-(三氟甲基)-2-吡啶甲酸的黄光铱配合物的合成、光物理性质及量化计算研究

利用环金属配体2-(2’,4’-二氟苯基)-4-甲基吡啶(dfpmpy)和辅助配体5-(三氟甲基)-2-吡啶甲酸(tfmpic)合成了一个铱配合物[Ir(dfpmpy)₂(tfmpic)],并测定了该配合物的光物理和电化学性质。在乙腈溶液中,配合物发射黄色磷光,其最大波长位于554 nm,理论计算表明其磷光来自于金属和环金属配体到辅助配体的电荷转移跃迁(₃MLCT 或 ₃LLCT)。     

蓝色磷光嘧啶铱(Ⅲ)配合物的合成、晶体结构及发光性能

合成了一种铱配合物[Ir(N4)(MDFPPM)2](MDFPPM=4,6-二甲基-2-(2,4-二氟苯基)嘧啶,N4=5-(2-吡啶基)-1H-四唑),并利用X射线单晶衍射仪测定了该化合物的2种晶体结构。通过紫外-可见(UV-Vis)吸收光谱、荧光光谱、循环伏安法及含时密度泛函理论(TD-DFT)对其光物理性能及能级结构进行了研究。结果表明:2个晶体的空间构型均为单斜,空间群均为P21/c;Ir(N4)(MDFPPM)2的最高占据轨道(HOMO)主要定域于金属Ir(Ⅲ)和配体MDFPPM的苯环上,最低未占有轨道(LUMO)主要定域于配体MDFPPM的嘧啶环上;配合物Ir(N4)(MDFPPM)2的HOMO和LUMO能级分别为-5.98和-3.22 e V;Ir(N4)(MDFPPM)2在77 K乙腈溶液中的发射峰波长在449、480和513 nm,CIEx,y色度坐标为(0.15,0.23),是一种潜在的蓝色磷光材料。     

利用吡啶衍生物主配体共轭效应调控铱配合物发光颜色

利用2-苯基吡啶及其衍生物为主配体、四苯基膦酰亚胺为辅助配体合成了3个铱配合物Ir（ppy）₂tpip（Hppy：2-苯基吡啶,Htpip：四苯基膦酰亚胺）、Ir（npy）₂tpip（Hnpy：2-（1-萘基）吡啶）和Ir（pnpy）₂tpip（Hpnpy：2-（9-菲基）吡啶）。它们的结构通过1HNMR和MALDI-TOF质谱进行了表征,其中配合物Ir（ppy）₂tpip还进一步通过晶体结构分析验证。主配体从苯环到萘环和菲环的改变增加了配合物的π共轭,减小了能级差,导致了3种配合物的磷光发射光谱从516nm红移到600和633nm（从绿光到红光）,发光量子效率也从0.36增加到0.51和0.53。从量化计算的结果可以看出,这种共轭效应增加了主配体的电子密度,提高了配合物的LUMO能级。配合物结构和发射性质之间的关系规律为设计不同发光颜色的铱配合物提供了思路。     

离子型嘧啶铱(Ⅲ)配合物的合成、晶体结构及发光性能

以嘧啶类化合物为环金属配体,2,2′-联吡啶为副配体成功制备了4种离子型环金属铱配合物:[(PPM)_2Ir(bpy)]PF_6(1),[(MPPM)2_Ir(bpy)]PF_6(2),[(DFPPM)_2Ir(bpy)]PF_6(3),[(MDFPPM)_2Ir(bpy)]PF_6(4)(PPM=2-苯基嘧啶,MPPM=4,6-二甲基-2-苯基嘧啶,DFPPM=2-(2,4-二氟苯基)嘧啶,MDFPPM=4,6-二甲基-2-(2,4-二氟苯基)嘧啶,bpy=2,2′-联吡啶)。配合物的结构通过质谱、核磁进行了表征,测试了配合物4的单晶结构。通过紫外-可见(UV-Vis)吸收光谱、荧光光谱和含时密度泛函理论(TD-DFT)对其光物理性能进行了研究。结果表明:4的晶体的空间构型为单斜,空间群为P21/c;3和4的最高占据轨道(HOMO)主要定域于金属Ir(Ⅲ)和环金属配体的苯环上,最低未占有轨道(LUMO)主要定域于副配体bpy上;配合物在溶液状态下为绿光发射,波长在513~561nm之间,量子效率在6.7%~64.0%之间。     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.